The present invention relates to methods of dyeing a material, comprising contacting the material with dye intermediates in combination with an enzymatic oxidation system.
Dyeing of textiles is often considered to be the most important and expensive single step in the manufacturing of textile fabrics and garments. In the textile industry, two major types of processes, batch and continuous, are currently used for dyeing. In the batch process, among others, jets, drums, and vat dyers are used. In continuous processes, among others, padding systems are used. See, e.g., I. D. Rattee, In C. M. Carr (Ed.), xe2x80x9cThe Chemistry of the Textiles Industry,xe2x80x9d Blackie Academic and Professional, Glasgow, 1995, p. 276.
The major classes of dyes are azo (mono-, di-, tri-, etc.), carbonyl (anthraquinone and indigo derivatives), cyanine, di- and triphenylmethane and phthalocyanine. All these dyes contain chromophoric groups which give rise to color. Two classes of dyes, vat and sulfur dyes, are applied to materials by an oxidation/reduction mechansim. The purpose of the oxidation/reduction step is to change the vat or sulfur dyestuff between an insoluble and a soluble form.
The dominant chemical class of dyestuffs is azo dyes. Most commonly, azo dyestuffs are manufactured as the dye, then applied to a material to color the material. In a variation of this technology, known as azoic dyeing, coupling between the strongly electrophilic diazonium ion and a nucleophilic compound leads to formation of colored azo compounds in situ on the material. The mechanism and process for azoic dyeing are described, for example, in Colorants and Auxiliaries, Volume 1xe2x80x94Colorants, Society of Dyers and Colourists, West Yorkshire, England, 1990 and Cellulosics Dyeing, Society of Dyers and Colourists, West Yorkshire, England, 1995.
Oxidoreductases, e.g., oxidases and peroxidases, are well known in the art.
One class of oxidoreductases is laccases (benzenediol:oxygen oxidoreductases) which are multi-copper containing enzymes that catalyze the oxidation of phenols and related compounds. Laccase-mediated oxidation results in the production of aromatic radical intermediates from suitable substrates; the ultimate coupling of the intermediates so produced provides a combination of dimeric, oligomeric, and polymeric reaction products. Such reactions are important in nature in biosynthetic pathways which lead to the formation of melanin, alkaloids, toxins, lignins, and humic acids.
Another class of oxidoreductases are peroxidases, which oxidize compounds in the presence of hydrogen peroxide.
Laccases have been found to be useful for hair dyeing. See, e.g., PCT applications Serial No. PCT/US95/06815 and PCT/US95/06816. European Patent No. 0504005 discloses that laccases can be used for dyeing wool at a pH in the range of between 6.5 and 8.0.
Saunders et al., Peroxidase, London, 1964, p. 10 ff. discloses that peroxidases act on various amino and phenolic compounds resulting in the production of a color.
Kunz et al., U.S. Pat. No. 5,849,041, discloses a hair dyeing composition containing a combination of aromatic diamine, e.g. 1,4-phenylenediamine (developer), xcex1-naphthol (coupler), an oxygen-oxido-reductase/substrate system and a peroxidase. Kunz further teaches that the preferred coupler substance comprises a substituted m-phenylenediamine.
French Patent 2,112,549 discloses dyeing hair with an aqueous solution containing oxidase enzyme and aromatic compounds, such as aromatic diamines, phenols, and derivatives of these, that are precursors for oxidative color. Sulfonated and carboxylated aromatic diamines and phenols are disclosed. The use of laccase is disclosed.
Roure et al., European Patent 504,005, discloses that 1-naphthol (xcex1-naphthol), 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene are known oxidative couplers for hair dyeing that can be used in combination with aromatic diamines, such as 1,4-phenylenediamine and N-phenyl-1,4-phenylenediamine, and with laccase enzyme.
Peck, U.S. Pat. No. 2,539,202 discloses a method of dyeing animal fibers, such as fur, animal pelts, and the like, comprising the steps of applying to the animal fibers an aqueous solution of a tyrosine or dioxyphenylalanine propigment followed by applying an oxidase, such as tyrosinase or polyphenolase.
Soloway, U.S. Pat. No. 3,251,742 discloses a method for coloring hair using a polyhydric aromatic compound, aromatic amine, and an oxidation enzyme.
Yaver et al., U.S. Pat. No. 5,667,531 discloses a dye composition for dyeing hair, wherein the composition contains a laccase and a dye precursor and optional coupler of the types disclosed by Soloway (e.g., phenylenediamine and aminophenol).
Japanese Patent Application publication no. 6-316874 discloses a method for dyeing cotton comprising treating the cotton with an oxygen-containing medium, wherein an oxidation reduction enzyme selected from ascorbate oxidase, bilirubin oxidase, catalase, laccase, peroxidase, and polyphenol oxidase is used to generate the oxygen.
WO 91/05839 discloses that oxidases and peroxidases are useful for inhibiting the transfer of textile dyes.
However, none of these citations suggests or discloses the use of combinations of dye intermediates in which at least one intermediate is an aromatic diamine and at least one intermediate is either a naphthol or an aminonaphthalene, in combination with an oxidizing enzyme, particularly when the naphthol is anything other than unsubstituted xcex1(alpha)-naphthol, halogenated 1-naphthol, or unsubstituted dihydroxynapthalene, or when one or more of the dye intermediates is substituted with a sulfonic acid (or salt thereof), a carboxylic acid (or salt thereof), a sulfonamide, or a quaternary ammonium salt.
Thus, there is a need in the art for improved enzymatic methods for dyeing textile materials.
The present invention provides a method of dyeing a material, which is carried out by contacting the material with a dyeing system which comprises:
(a) a mixture of dye intermediates comprising (i) at least one aromatic diamine and (ii) at least one compound selected from a naphthol and an aminonaphthalene; and
(b) an oxidation system comprising (i) a hydrogen peroxide source and an enzyme exhibiting peroxidase activity or (ii) an enzyme exhibiting oxidase activity on one or more of the compounds of mixture (a), under conditions in which a colored material is produced or the color is altered. In some embodiments, at least one of the compounds of (a)(i) or (a)(ii) is substituted with a sulfonic acid (or salt thereof), a carboxylic acid (or salt thereof), a sulfonamide, or a quaternary ammonium salt. In some embodiments, the naphthol is any naphthol other than xcex1(alpha)-naphthol (also referred to as 1-naphthol), halogenated 1-naphthol, or unsubstituted dihydroxynaphthalene. In some embodiments, either (a) the aromatic diamine is substituted with a functional group selected from the group consisting of a sulfonic acid, a carboxylic acid, a salt of a sulfonic acid or carboxylic acid, a sulfonamide, and a quaternary ammonium salt or (b) the naphthol is not unsubstituted xcex1(alpha)-naphthol, halogenated 1-napthol, or an unsubstituted dihydroxynaphthalene. Preferably, the enzyme is a peroxidase or a laccase.
The presence of the above-cited substituent groups on at least one compound of the dye intermediate mixture improves ease of handling of the dye intermediate compounds, facilitates dyeing of the materials, and improves color performance properties, such as, e.g., by decreasing wash staining.
The materials to be dyed include, without limitation, a fabric, yam, fiber, garment or film made of fur, hide, leather, silk, wool, cationic polysaccharide, cotton, diacetate, flax, linen, lyocel, polyacrylic, synthetic polyamide, polyester, ramie, rayon, triacetate, or viscose.
In some embodiments, the aromatic diamine is a compound of formula A, the naphthol is a compound of formula B, and the aminonaphthalene is a compound of formula C as shown below: 
wherein X may independently be hydrogen, sulfonic acid, carboxylic acid, a salt of sulfonic acid, a salt of carboxylic acid, sulfonamide, or a quaternary ammonium salt; R1 and R2 may each independently be one of hydrogen, C1-18-alkyl, C1-18-hydroxyalkyl, phenyl, aryl, azobenzene, amidophenyl, azobenzene substituted with one or more functional groups, and amidophenyl substituted with one or more functional groups; and the remaining positions on the aromatic ring(s) of A, B, and C are optionally substituted with one or more functional groups, including, without limitation, hydrogen, halogen, sulfo, sulfonato, sulfamino, sulfanyl, amino, amido, amidoaryl, nitro, azo, azoaryl, imino, carboxy, cyano, formyl, hydroxy, halocarbonyl, carbamoyl, carbamidoyl, phenyl, aryl, phosphonato, phosphonyl, C1-18-alkyl, C2-18-alkenyl, C2-18-alkynyl, C1-18-alkoxy, C1-18-oxycarbonyl, C1-18-oxoalkyl, C1-18-alkyl sulfanyl, C1-18-alkyl imino, and amino which is substituted with one, two, or three C1-18-alkyl groups. In some embodiments, the halogen may be one of fluorine, chlorine, bromine or iodine.
In other embodiments, the naphthol may be a compound of formula D 
wherein X may independently be hydrogen, sulfonic acid, carboxylic acid, a salt of sulfonic acid, a salt of carboxylic acid, sulfonamide, or a quaternary ammonium salt and the remaining positions on the aromatic rings of D are one or more functional groups, including, without limitation, hydrogen, halogen, sulfo, sulfonato, sulfamino, sulfanyl, amino, amido, amidoaryl, nitro, azo, azoaryl, imino, carboxy, cyano, formyl, hydroxy, halocarbonyl, carbamoyl, carbamidoyl, phenyl, aryl, phosphonato, phosphonyl, C1-18-alkyl, C2-18-alkenyl, C2-18-alkynyl, C1-18-alkoxy, C1-18-oxycarbonyl, C1-18-oxoalkyl, C1-18-alkyl sulfanyl, C1-18-alkyl imino, and amino which is substituted with one, two, or three C1-18-alkyl groups. In some embodiments, the halogen may be one of fluorine, chlorine, bromine or iodine.
Examples of aromatic diamines useful in practicing the present invention include, without limitation, 2-methoxy-p-phenylenediamine, N,N-bis-(2-hydroxyethyl)-p-phenylenediamine, N-xcex2-methoxyethyl-p-phenylenediamine, 2-methyl-1,3-diamino-benzene, 2,4-diaminotoluene, 2,5-Diaminotoluene, 2,6-diaminopyridine, 1-N-methylsulfonato-4-aminobenzene, 1-methoxy-2,4-diamino-benzene, 1-ethoxy-2,3-diamino-benzene, 1-xcex2-hydroxyethyloxy-2,4-diamino-benzene, 1,4-Phenylenediamine, 2-Chloro-1,4-phenylenediamine, 1,3-Phenylenediamine, 2,3-diaminobenzoic acid, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, methyl-2,3-diaminobenzate ethyl-2,3-diaminobenzoate, isopropyl-2,3-diaminobenzoate, methyl-2,4-diaminobenzoate, ethyl-2,4-diaminobenzoate, isopropyl 2,4-diaminobenzoate, methyl-3,4-diaminobenzoate, ethyl-3,4-diaminobenzoate, isopropyl-3,4-diaminobenzoate, methyl-3,5-diaminobenzoate, ethyl-3,5-diaminobenzoate, isopropyl-3,5-diaminobenzoate, N,N-dimethyl-3,4-diaminobenzoic acid amide, N,N-diethyl-3,4-diaminobenzoic acid amide, N,N-dipropyl-3,4-diaminobenzoic acid amide, N,N-dibutyl-3,4-diaminobenzoic acid amide, N-phenyl-p-phenylenediamine, Disperse Black 9, Solvent Brown 1 (CI 11285), 4,4xe2x80x2-Diaminodiphenylamine sulfate, 4-aminodiphenlyamine-2-sulfonic acid, N-(4xe2x80x2-aminophenyl)aminobenzene-4-sulfonic acid, N,N-dimethyl-1,4-phenylenediamine, N,N-diethyl-1,4-phenylenediamine, Disperse Yellow 9, N-phenyl-1,2-phenylenediamine, 1,2-phenylenediamine, and 4xe2x80x2-aminoacetanilide, and N-phenyl-2-aminobenzene-4-sulfonic acid, N-(4xe2x80x2-aminophenyl)-aminobenzene-4-sulfonic acid, 2,3-diaminobenzenesulfonic acid, 2,4-diaminobenzenesulfonic acid 2,5-diaminobenzenesulfonic acid, 3,5-diaminobenzenesulfonic acid, and 3,4-diaminobenzenesulfonic acid.
Useful naphthols include, without limitation, 4-Chloro-1-naphthol, 4-Bromo-1-naphthol, 4-Methoxy-1-naphthol, 2-Nitroso-1-naphthol, 1-Naphthol-3-sulfonamide, and 1-Naphthol-8-sulfonamide, 4,8-Disulfonato-1-naphthol, 3-Sulfonato-6-amino-1-naphthol, 6,8-Disulfonato-2-naphthol, 4,5-Dihydroxynapthalene-2,7-disulfonic acid, 2-Amino-8-naphthol-6-sulfonic acid, 5-Amino-1-naphthol-3-sulfonic acid, 2-Naphthol-3,6-disulfonic acid, 1-Amino-8-naphthol-2,4-disulfonic acid, 1-Naphthol-4-sulfonic acid, N-Benzoyl J acid, N-Phenyl J acid, Mordant Black 3 (CI 14640), 4-Amino-5-hydroxy-2,6-naphthalene disulphonic acid, Acid Black 52 (CI 15711), Palantine Chrome Black 6BN (CI 15705), Eriochrome Blue Black R, Mordant Black 11, Eriochrome Black T, Naphthol Blue Black, Acid Black 1 (CI 20470), Acid Red 176 (CI 1657), Acid Red 29 (CI 16570), Acid Red 14 (CI 14720), and 1-Naphthol-3-sulfonic acid.
Useful aminonapthalenes include, without limitation, 1-Amino-8-hydroxynaphthalene-4-sulfonic acid, 2-Amino-8-naphthol-6-sulfonic acid, 5-Amino-1-naphthol-3-sulfonic acid, 1-Amino-8-naphthol-2,4-disulfonic acid, 8-Amino-1-naphthalenesulfonic acid, 8-Anilino-1-naphthalenesulfonic acid, 8-Amino-2-naphthalenesulfonic acid, 5-Amino-2-naphthalenesulfonic acid, 4-Amino-5-hydroxy-2,6-naphthalenedisulphonic acid, 2,3-Diaminonaphthalene, 1,5-Diaminonaphthalene, 1,8-Diaminonaphthalene, 6-Amino-2-naphthol, 3-Amino-2-naphthol, 5-Amino-1-naphthol, Acid Black 1 (CI 20470), 4-Amino-1-naphthalenesulfonic acid, 6-(p-Toluidino)-2-naphthalenesulfonic acid, 1,4-Diamino-2-naphthalenesulfonic acid, and 5,8-Diamino-2-naphthalenesulfonic acid.
In practicing the invention, the material may be contacted simultaneously with the dye intermediates, enzyme, and electron acceptor. In another embodiment, the material may be contacted with one or both of the dye intermediates, after which the second dye intermediate (where applicable), enzyme, and electron acceptor are added. In yet another embodiment, the material is first contacted with the enzyme, after which the dye intermediates and electron acceptor are added.
In preferred embodiments, the methods of the invention provide dyed materials having an activation ratio (AR) of at least 0.25, preferably at least 1, and most preferably at least 2, where AR is defined as: AR=(L* controlxe2x88x92L* enzyme)/L* enzyme and the dye intermediates are used at an aggregate concentration of about 5% o.w.g. (of weight of goods).
In another aspect, the invention provides dyes produced using the methods described herein.
In another aspect, the invention provides dyeing kits comprising:
(a) at least one aromatic diamine;
(b) at least one of a naphthol and an aminonaphthalene; and
(c) one or more of a peroxidase and a laccase.
In some embodiments, the aromatic diamine in the kit is substituted with a sulfonic acid (or salt thereof), a carboyxlic acid (or salt thereof), a sulfonamide, or a quaternary ammonium salt. In preferred embodiments, at least one of the aromatic diamine, naphthol, and aminonaphthalene is substituted with a sulfonic acid (or salt thereof), a carboyxlic acid (or salt thereof), a sulfonamide, or a quaternary ammonium salt. In some embodiments, the naphthol in the kit is any naphthol other than xcex1(alpha)-napthol, halogenated 1-naphthol, or unsubstituted dihydroxynaphthalene. In some embodiments, either (a) the aromatic diamine is substituted with a functional group selected from the group consisting of a sulfonic acid, a carboxylic acid, a salt of a sulfonic acid or carboxylic acid, a sulfonamide, and a quaternary ammonium salt or (b) the naphthol is not unsubstituted xcex1(alpha)-naphthol, halogenated 1-napthol, or an unsubstituted dihydroxynaphthalene. In preferred embodiments, the aromatic diamine is one of: 1,4-Phenylenediamine, N-Phenyl-p-phenylenediamine, N,N-Diethyl-1,4-phenylenediamine, 4-aminodiphenylamine-2-sulfonic acid, N-(4xe2x80x2-aminophenyl)aminobenzene-4-sulfonic acid, and 2-5-diaminobenzenesulfonic acid; the naphthol or aminonaphthalene is one of 1-Naphthol-4-sulfonic acid, N-Phenyl J acid, 8-amino-1-naphthalenesulfonic acid, 8-anilino-1-naphthalenesulfonic acid, 8-amino-2-naphthalenesulfonic acid, and 5-amino-2-naphthalenesulfonic acid; and the oxidation enzyme is a laccase.